Process and means for oxidized dyeing of hair using a manganese dioxide catalyst

ABSTRACT

In a process for the oxidative dyeing of human or animal hair, a hair dyeing agent is prepared immediately before use from at least one oxidation dye and an oxidizing agent, applied to the hair to be dyed, and made to act for a given period of time, whereupon the hair dyeing agent is washed out. The hair dyeing agent that is to be used is prepared from an oxidation dye and the oxidizing agent with the concomitant use of manganese dioxide in powder form, while the finished hair dyeing agent is adjusted to a weakly acid pH in the range from 5.9 to 6.9.

The invention relates to a process for the oxidized dyeing of human oranimal hair, in which a hair dyeing agent is prepared immediately beforeuse from at least one oxidation dye and one oxidizing agent, applied tothe hair that is to be dyed, and made to act for a given period of time,whereupon the hair dyeing agent is washed out, as well as a hair dyeingagent for performing the process.

For the lasting dyeing of human hair, alkaline oxidation dyes in pasteform are used, which are mixed immediately before use with an acidoxidizing agent, e.g., hydrogen peroxide, to form the ready-to-use hairdyeing preparation that is to be applied to the hair being dyed. Thecolor is produced by the reaction of certain developer substances withcertain coupling substances in the presence of a suitable oxidizingagent. The ready-to-use preparation in this case is definitely in thealkaline range, so that the surfaces of the hairs to be dyed are openedup advantageously for the penetration of the oxidation dyes. On theother hand, alkaline preparations also are stressful to the hair, sothat, especially when they are used repeatedly, e.g., for repeatedredyeing, they can harm the hair. Such redyeing, however, is necessary,especially in the case of light-colored hair, in order, for example, tomatch the undyed regrowth to the color of the previously dyed hairlengths, or to refresh the color of the previously dyed hair lengths ifthe original color has faded in the course of time due to otherinfluences, such as sunshine, frequent washing and the like.

Attempts to prevent the harmful effects, especially at the hair ends, ofalkaline hair dyeing agents by acidifying the preparations ready-madefrom the oxidation dye and the oxidizing agent have led to insufficientcoloring of the hair and therefore have not been further pursued.

The invention is addressed to the problem of devising a process for theoxidizing dyeing of hair as well as the hair dyeing agent necessary forthe purpose, which, even when frequently used, will not result in thehair damage described above.

Setting out from a process of the kind described above, this object isachieved according to the invention by the use of a hair dyeing agentprepared in powder form from an oxidation dye and oxidizing agents withthe use of manganese dioxide, and adjusted to a weakly acid pH in therange from 5.9 to 6.9. It has been found that, when such a hair dyeingagent with a weakly acid adjustment is used in the company of manganesedioxide, outstandingly persistent dyeing of human hair in bright shadesis possible, unless darker hair is to be redyed to a lighter shade. Thesuccessful dyeing action, in comparison to earlier experiments with acidhair dyeing agents, is attributed to the catalytic action of themanganese dioxide contained in the hair dyeing agent. Furthermore it wasfound that the hair damage which was to be attributed to the alkalinityof the previously used hair dyeing agents is completely avoided.

From the above information it appears that, for the lightening orbrightening of darker hair, recourse must be had to the known alkalinehair dyeing agents. Since damage to the hair is produced by suchalkaline hair dyeing agents as a rule only after repeated redyeing, suchdamage can be prevented if, in the redyeing of hair dyed to a lightercolor, which in the natural state is darker, the procedure is first toemploy a known hair dyeing agent of alkaline adjustment on the darkerregrowth close to the scalp, but in the adjoining, previously dyed hairlengths to apply the weakly acid hair dyeing agent, and to wash both thealkaline and the weakly acid hair dyeing agents out of the treated hairafter a sufficient time of action.

Especially problematical in regard to hair damage is a combinedpermanent wave and hair dyeing treatment. In a process for the wavingand oxidation dyeing of hair in which first a permanent-wave preparationis made to act for a given period of time on the hair washed and woundon curlers, and then washed out, and then the still-wound hair ispre-fixed with a liquid oxidizing fixing agent, and lastly the hair isfreed from the curlers and refixed in an additional treatment step withan oxidizing fixing agent, the danger of hair damage is substantiallyreduced by using the weakly acid hair dyeing agent for the secondfixing, letting it act on the hair for the length of time necessary forthe sufficient coloring of the hair, and then washing it out. The hairdyeing agent therefore replaces the fixing agent used ordinarily inpermanent waving for the second fixing, i.e., it serves a doublepurpose, while the damage to be feared in the use of alkaline hairdyeing means is avoided.

The hair dyeing agent used in the process according to the invention,which is prepared before application from an oxidizing dye and anoxidizing agent--liquid as a rule--can be produced by adding themanganese dioxide powder to the oxidizing dye before the addition of theoxidizing agent.

Alternatively, the manganese dioxide powder can be added simultaneouslywith or immediately after the oxidizing dye is mixed with the oxidizingagent in the preparation of the hair dyeing agent. The addition ofmanganese dioxide powder to the hair dyeing agent in such an amount thatit is contained in the hair dyeing agent in a percentage between 0.02and 5 weight-percent, preferably between 0.12 and 0.18 weight-percent,has proven to be of optimum effectiveness.

The preparation produced by mixing an oxidizing dye with an oxidizingagent immediately before use in the performance of the process accordingto the invention is therefore characterized by being adjusted to a pHbetween 5.9 and 6.9, and additionally contains finely divided manganesedioxide in powder form.

The amount of the manganese dioxide is preferably such that it iscontained in the hair dyeing agent in percentages between 0.02 and 5weight-percent, preferably between 0.12 and 0.18 weight-percent.

EXAMPLE 1a Oxidation Dyeing

20 ml of dye paste of the formula given below for the color, hazelnutblonde, with the addition of 0.12% of manganese(IV) oxide in finelydivided form, was mixed with 40 ml of a developer solution containing 2%of hydrogen peroxide, resulting in a hair dyeing agent with a pH of 6.7.The agent was applied to a medium-weight hair with a medium ash-blondebasic shade, and allowed to act for 20 minutes.

The result was a recoloring of the hair to an intense hazelnut blondeshade.

Experiments showed that the time of action of the hair dyeing agent canbe reduced to 5 minutes with a correspondingly lower resultant colorintensity.

    ______________________________________                                        Formula of the "Hazelnut Blonde" Dye Paste:                                   ______________________________________                                        cetylstearyl alcohol     10.0 g                                               coconut fatty acid monoethanolamide                                                                    2.0 g                                                stearic acid monoethanolamide                                                                          2.0 g                                                stearic acid diethanolamide                                                                            1.0 g                                                p-toluylenediamine sulfate                                                                             0.25 g                                               m-aminophenol            0.01 g                                               resorcinol               0.01 g                                               p-aminophenol            0.08 g                                               p-amino-o-cresol         0.06 g                                               picraminic acid          0.05 g                                               monoethanolamine         0.2 g                                                ammonium chloride        0.2 g                                                sodium lauryl sulfate    0.3 g                                                manganese(IV) oxide      0.12 g                                               sodium sulfite           0.2 g                                                ethylenediaminetetraacetic acid                                                                        0.2 g                                                perfume                  0.2 g                                                softened water to make   100.00 g                                             ______________________________________                                    

EXAMPLE 1b Oxidizing Dye

20 ml of the dye paste of the formula given below for the color "CopperBlonde" with the addition of 0.12% of manganese(IV) oxide in finelydivided form was mixed with 40 ml of a developer solution containing 2%of hydrogen peroxide, resulting in a hair dyeing agent with a pH of 6.7.

The dyeing agent was applied to a medium-weight hair with a mediumash-blonde basic shade and allowed to act for 20 minutes.

As a result the hair was dyed to a discreet copper shade.

Experiments showed that the time of action of the hair dyeing agent canbe shortened to only 5 minutes with a correspondingly reduced resultantcolor intensity.

    ______________________________________                                        Formula for the "Copper Blonde" Dye Paste                                     ______________________________________                                        cetylstearyl alcohol     10.0 g                                               coconut fatty acid monoethanolamide                                                                    2.0 g                                                stearic acid monoethanolamide                                                                          2.0 g                                                stearic acid diethanolamide                                                                            1.0 g                                                p-toluylenediamine sulfate                                                                             0.20 g                                               p-aminophenol            0.70 g                                               p-amino-o-cresol         0.70 g                                               monoethanolamine         0.2 g                                                ammonium chloride        0.2 g                                                sodium laurylsulfate     0.3 g                                                manganese(IV) oxide      0.12 g                                               sodium sulfite           0.12 g                                               ethylenediaminetetraacetic acid                                                                        0.2 g                                                perfume                  0.2 g                                                softened water to make   100.00 g                                             ______________________________________                                    

EXAMPLE 2 Oxidation Dyeing for a Gentle, Acid Equalization of the HairEnds After a Normal, Alkaline Initial Dyeing

20 ml of dye paste of the formula given in Example 1a for the hair color"Hazelnut Blonde" with an addition of 0.12% of manganese(IV) oxide infinely divided form, was mixed with 40 ml of a developer solutioncontaining 2% of hydrogen peroxide, resulting in a hair dye with a pH of6.7.

The dye was applied to a medium-heavy hair which had been dyed hazelnutblonde and whose lengths and ends had faded and had a light ash blondetone, and allowed to act for 10 minutes.

As a result, a hazelnut blonde shade equalized with the initial dye ofthe bleached lengths and ends was obtained. The time of action of thepreparation can be shortened to 5 minutes at lesser equalizing colorintensities.

EXAMPLE 3a Oxidation Dyeing Combined with Permanent Waving

A permanent wave was performed on medium-heavy hair which had a basiccolor of dark golden blonde, and in which the hair lengths and ends hadfaded.

The permanent wave was performed on the curler according to instructionsup to and including the first fixing.

For the final fixing and simultaneous dyeing, the curler was removed and20 ml of dye paste of the formula given below for the color, "cyclamen,"with an addition of 0.12% of manganese(IV) oxide in finely divided form,was mixed with 40 ml of a permanent wave fixer with a hydrogen peroxidecontent of 2%.

The resultant hair dyeing agent with a pH of 6.7 was then applied to thehair with an applicator bottle and a sponge and allowed to work for 10minutes. The result was a redyeing of the hair to a reddish violet(cyclamen) shade in addition to the permanent wave. The working time canbe varied between 5 and 20 minutes according to the desired colorintensity.

    ______________________________________                                        Formula for "Cyclamen" Hair Dye Paste                                         ______________________________________                                        cetylstearyl alcohol     10.0 g                                               coconut fatty acid monoethanolamide                                                                    2.0 g                                                stearic acid monoethanolamide                                                                          2.0 g                                                stearic acid diethanolamide                                                                            1.0 g                                                p-toluylenediamine sulfate                                                                             0.5 g                                                p-amino-o-cresol         0.4 g                                                p-aminophenol            0.1 g                                                monoethanolamine         0.2 g                                                ammonium chloride        0.2 g                                                sodium lauryl sulfate    0.3 g                                                manganese(IV) oxide      0.12 g                                               sodium sulfite           0.25 g                                               ethylenediaminetetraacetic acid                                                                        0.2 g                                                perfume                  0.2 g                                                softened water to make   100.0 g                                              ______________________________________                                    

EXAMPLE 3b Oxidation Dyeing Combined with Permanent Wave

A permanent wave was performed on medium-heavy hair which had a basiccolor of golden blond and in which the hair lengths and ends had faded.

The permanent wave was performed on the curler according to instructionsup to and including the first fixing.

For the second fixing and simultaneous dyeing, the curlers were removedand 20 ml of dye paste of the formula given below for the color"Mahogany" with the addition of 0.12% manganese(IV) oxide in finelydivided form was mixed with 40 ml of a permanent wave fixer with ahydrogen peroxide content of 2%.

The resultant hair dyeing agent with a pH of 6.7 was then applied to thehair with an applicator bottle and a sponge swab and allowed to work for10 minutes. As the result, the hair was redyed to a strong red shade inaddition to the permanent wave. The working time can be varied between 5and 20 minutes according to the desired color intensity.

    ______________________________________                                        Formula for "Mahogany" Dye Paste                                              ______________________________________                                        cetylstearyl alcohol     10.0 g                                               coconut fatty acid monoethanolamide                                                                    2.0 g                                                stearic acid monoethanolamide                                                                          2.0 g                                                stearic acid diethanolamide                                                                            1.0 g                                                p-toluylenediamine sulfate                                                                             0.4 g                                                p-aminophenol            0.4 g                                                p-amino-o-cresol         0.4 g                                                o-nitro-p-phenylenediamine                                                                             0.4 g                                                monoethanolamine         0.2 g                                                ammonium chloride        0.2 g                                                sodium lauryl sulfate    0.3 g                                                manganese(IV) oxide      0.12 g                                               sodium sulfite           0.25 g                                               ethylenediaminetetraacetic acid                                                                        0.2 g                                                perfume                  0.2 g                                                softened water to make   100.0 g                                              ______________________________________                                    

We claim:
 1. A method of dyeing human or animal hair, comprising thesteps of: preparing a dyeing agent having a pH between 5.9 and 6.9, froma mixture of approximately one-third by weight of an aqueous oxidationdye paste containing an effective amount of an oxidation dye, andapproximately two-thirds by weight of a developer solution containingapproximately two percent of hydrogen peroxide, and 0.02 to 5 percent byweight of powdered manganese dioxide as a catalyst; immediatelythereafter applying said dyeing agent to the hair and letting the sameact on the hair for a period of time sufficient to dye the hair; andwashing the dyeing agent out of the hair.
 2. A method of re-dyeing humanor animal hair which in natural state is dark and has previously beendyed to a lighter state, comprising the steps of: applying a firstconventional alkalinely adjusted hair dyeing agent to recent growth ofdarker hair close to the scalp, preparing a second dyeing agent having apH between 5.9 and 6.9, from a mixture of approximately one-third byweight of an aqueous oxidation dye paste containing an effective amountof an oxidation dye, and approximately two-thirds by weight of adeveloper solution containing approximately two percent of hydrogenperoxide, and 0.02 to 5 percent by weight of powdered manganese dioxideas a catalyst; immediately thereafter applying said dyeing second agentto the lighter state hair adjacent to the recent growth of hair andletting the same act on the lighter state hair for a period of timesufficient to dye the hair; and washing both dyeing agents out of thehair.
 3. A method of waving and dyeing human or animal hair, comprisingthe steps of: applying a conventional permanent-wave preparation to thehair, which has previously been washed and wound on curlers, for a givenperiod of time, washing out the hair, fixing the hair, still wound onthe curlers, with a conventional liquid oxidizing fixing agent; removingthe curlers, and re-fixing the hair with a dyeing agent having a pHbetween 5.9 and 6.9, from a mixture of approximately one-third by weightof an aqueous oxidation dye paste containing an effective amount of anoxidation dye, and approximately two-thirds by weight of a developersolution containing approximately two percent of hydrogen peroxide, and0.02 to 5 percent by weight of powdered manganese dioxide as a catalyst;letting the dyeing agent act on the hair for a period of time sufficientto dye the hair, and washing the dyeing agent out of the hair.
 4. Amethod according to any one of claims 1 to 3, wherein the percentage ofthe powdered manganese dioxide is 0.12 to 0.18.
 5. A method of preparinga dyeing agent for human or animal hair, comprising the steps of: mixingapproximately one-third by weight of an aqueous oxidation dye pastecontaining an effective amount of an oxidation dye, and approximatelytwo-thirds by weight of a developer solution containing approximatelytwo percent of hydrogen peroxide, and 0.02 to 5 percent by weight of apowdered manganese dioxide as a catalyst so as to result in a dyeingagent having a pH between 5.9 and 6.9.
 6. A method according to claim 5,wherein the percentage by weight of the powdered manganese dioxide is0.12 to 0.18.
 7. A method according to claim 5, wherein the manganesedioxide is mixed with the oxidation dye, prior to the addition of theoxidizer.
 8. A method according to claim 5, wherein the manganesedioxide is mixed with the oxidation dye, after the addition of theoxidizer.
 9. A method according to claim 5, wherein the manganesedioxide is mixed with the oxidation dye, simultaneously with theaddition of the oxidizer.
 10. An agent for dyeing human or animal hair,comprising: a mixture of approximately one-third by weight of an aqueousoxidation dye paste containing an effective amount of an oxidation dye,and approximately two-thirds by weight of a developer solutioncontaining approximately two percent of hydrogen peroxide, and 0.02 to 5percent by weight of powdered manganese dioxide as a catalyst; saidagent having a pH between 5.9 and 6.9.
 11. An agent according to claim10, wherein the percentage by weight of the powdered manganese dioxideis 0.12 to 0.18.